New condensation products and a process for preparing same



" Patented Feb, 9, 1931 -ui-m'1;o srArEs. PATENT -,o1=rlcs 'aeremf NEW CONDENSAHON PRODUCTS AND A r PROCESS FOR PREPABINGSAMI Johann Buismann and mm Schweitner, Wlean derl, near Cologne-on-the-Bhine, Gummy altimmtoLQFar t, Irnnktort-en-the-Main,

mm to. 1m.

In Germany llarob 8.. me

We Germany; a

Serial 1 anim- '(ci. see -12o) v The present invention new condensationproducts and to a process for preparing same; more particularly it relates to compounds oi the probable general iormulazm ntal-morass;

1 wherein Y stands for an aromatic radical. such as for instance, of the benzene, naphthalene or diphenyl series. in which latter the benzenenuclei may also be iinkedwith each other by means of a bridge, for example for the group.

15 iing-c.r-ncn=cnc.rn, -Osnt-o-c.m-. the above mentioned nuclei being substituted by .asultonic acid group, Ac stands, for S0: or

00, "m" and (R-r" stand for aromatic nuclei of the benzene "series having the Ac and NH groups '20 attached to them in meta position to each other and "Re" and R4? stand for aromatic nuclei or the benzene or naphthalene series; said nuclei n: and Rs being substituted inmate-position to the amide groups by a substituent oi the group 'consietin'l of halogen and said sulfonic amide 'or carboxylic amide groups. n being OH. or 2 and each group. being attached tov the preceding aromatic nucleus through the nitrogen atom or the amide All nuclei may be further substituted by chlorine or methyl groups.

"The new condensation products are obtainable by combining an aromatic sinionicacid halide or carboxylic acid halide with an aromatic diamine to term a water soluble sulionic acid amideor carboxylic acid amide-derivative. If the aromatic sulionie acid halide or the carboxylic acid halide contains a nitro group the same may be reduced to form an amino group and the condensation may be repeated with an aromatic acid halide. The reaction may be carried out in water in the presence oi an agent capable oLneutralisingthe hydrogen halide iormed i The new condensation productsv obtainable according to the new process are generalb colorless or nearly colorless',' water-soluble powders, and constitute valuable egents'tor reserving animal fibers, such aswool orsilk-and the like. against substantive The invention is illustrated by, the following" examples, without being limited a hours.

teredbysuction A Exam-pie 1.-l88 parts by weight of LS-phenyh enediamineA-sulionic acid are dissolved in about .20 times the weight or water with the addition weight of 2.5-dichlorobenaoyl chloride (110%0! the theoretical amount) The reaction temperature rises gradually to about C. and the re- 10 action product begins to separate in thick gran ular masses. It is advantageous to dilute the paste obtained by the addition of hot water. The mixture is gradually heated up to about 100 0., while thoroughly stirring, at which temperature the reaction mixture is maintained for several After cooling, the paste is filtered and stirred with hydrochloric acid until distinctly acid to Congo red. The crude product, alter filtering and washing with cold water isrediso solved from hot water and renderedalkaline by a the addition of sodium carbonate. There cryswhich is found to be an excellent agent tor reserving wool against substantive dyestuiis.

Example 2;--844 parts by weight of benzidinemni disulionlc acid are dissolved in about 30 times the weight of water with the addition of chalk; the mixture is stirred thoroughly at o 85- 0. in the presence or an excess of chalk or another acidjxlng agent with 563 parts by weight 0! B-chloro-i-tolueneA-suliochloride (125% or the quantity theoretically The temperature of the reaction mixture, raised 45 gradually to about C. and maintained there ior some hours; then the mixture is allowed to co6l,'and the precipitated reaction product is diin a hot sodium carbonate solution. iiltered. it 50 necessary, neutralized with hydrochloric acid and The crude product isdissolved precipitated by means of a sodium chloride solution. There is obtained in a satisfactory yield the sodium salt of the bis-(2-chloro-1-toluene-4-sul- -fonyl) benzldine-m.m'-disulfonic acid of the formula: i i

B OnNa which is a satisfactory s nt icireserving wool against substantive dyestuffs.

The 2-chloro-1-toluene-4-sulfochlorlde used in this example is obtained. for example, by introducing fl-chloro-l-toluene--sulfonic acid into about 5 times the quantity of sulfuric acidchlorhydrin andheating the resulting solution to 00-70 C. When the evolution" of the hydrochloric acid has ceased the reaction mixture is and, if necessary or desired, purified by dissolving then poured on to a freezing mixture, consisting of ice and sodium chloride, the precipitated i-chloro l-toluene-bsulfonic chloride is filtered in ether. It can be recovered from the driedx ethereal solution by distilling oil the ether.

trample 3.'--344 parts by weight of benzidine-i m.m'-disulfonic acid are dissolved in about 30 times the quantity'of water with the addition of chalk and stirred th temperaturesbetween 85 and 95 C. in theprescellent yield the sodium salt of the bis-(1.2.3-trlchlorobenzene-4-sulfonyl) ben zidine-m.m'-disulfonic acid;

OiNa 7 minst substantive dyestuffs.

The l.2.3 -tr 'ichlorobengcne-'4;sulfochloride used 'inthis exam le is obtained by introducin8 1.2.3-'-

sulfonic acid and slowly heating the sulfonatingmixture to about to 70" C." After the evolutrichlorobenseneinto 5 timesits weight of chloro tion or hydrochioric acid has ceased and cooling,

the mixture is poured on ice and the ups-mclilorobenzene 4-.sulfochloride, out in a granular form, is filtered oil. It, can be oboroughly for a long time at a yellowish colored which isan excellent agent for wool taineda pure state, by dissolving the crude.

product inrether, drying the solution with dried "calcium chloride,'and distilling oil the ether from the dry solution.v 1

trample 4,444 parts by weight of benzidinem.m'-dlsuli'onic acid are dissolved in hot water by means are weak sodium carbonate solution and treated. while thoroughly stirring, in the presence of an excess of chalk or sodium acetate or other acid flxingagents at '85-95" C. with 640 parts by weight of -nitro-l-chlorobenzene-iisulfochloride (125% of the theoretical amount).

'Aft'er heating for some-hours longer to about 100 C. and allowing to cool the-reaction product ls filtered by suction. It is dissolved in sodium carbonate solution, filtered, neutralized with dilute sulfuric acid and reduced by means of iron .with the addition of a little dilute sulfuric acid. Whenthe reduction is complete the reduction mixture is rendered alkaline with sodium carbonate and the hot'solution is filtered from the iron sludge. The solution is made acid by means of hydrochloric acid and again filtered while hot; the his -(4-amino-1-chlombenzene-2-sulfonyl) benzidine-m.m'-disulfonic acid:

crystallizes out.

The corresponding tetrazotized compound is and dii'iicultly soluble in cold water.. i

' (23' parts by weight offthe bis-(4-amino-l- .chlorobensene-2-suifonyl) benzidine disulfonic acid are dissolved by means of sodium carbonate solution, To the solution, heated to about 0.,

are added, while thoroughly stirring, 200 parts by weight of chalk and then 773 parts by weight of 1.2-dlchl'orobenzene-4 sulfo'chloride (150% of the theoretically necessary quantity) then the mixture is slowly heated to C. After A a short time the reaction product begins to separate in the form of a crust while the solution becomes clear. The temperature is then raised to about C.) andafter cooling and filtering the pulverized residue is made into a pastev by means ofdilute hydrochloric acid; the crude product is then separated by filtration from the .acid liquor, containing calcium chloride. The reactionproduct is dissolved by means of sodium carbonate'solution and precipitated with a little ;hydrochloric; acid, while m'aintalning the-'solution still alkaline. If necessary or desired, itcan .1 and then it is boiled for half an hour. The mixture is rendered weakiy'Congo acid with dilute be purified by 'redissolving mm m. It pile sesses the constitution:

B OIN.

l lw i v and protects wool exeellentLv against dyeing with I ly poured on to a freezing mixture, consisting .of sodium chloride and ice and the Lz-dichloro benzene-'l-sulfochlorlde is filtered oil; it necessary or desired, it can be purified by dissolving in ether, from which it can be recovered by distilling of! the ether alter drying the ethereal solution with calcium chloride.

Example 5.-344 parts by weight of benzidinem.m-disulionic acid are dissolved by heating in 1 10 to 15 times the quantity of water with the addition of 100 parts by weight oi chalk. To. this solution are added while stirring llioparts'by weight of chalk and at about 15 c. 532 parts by weight of meta-nitro-benzene-suliochloride whilst cooling.

r (120% of the theoretical amount); This reaction mixture is kept at 15-8020. ior some time hydrochloric acid and then the mass is stirred The bis-(3-nitrobenzene lt-sulionyl)-benzidine-m;m'-disulionic acid in the Ill-QB 05.1w I p t om:

form and may be mm on from the liquid by suction. It is redissolved in o to 10 times the quantity oi hot water and reduced by the addition 50 parts by volume oicrude hydrochloric acid. and 1000 parts by weight 01 iron powder; at a temperature or about 95-100, 0. maintained ior several hours. when the reduction is complete this" hot mixture is rendered strongly alka-,

line By the addition oi 525 parts by volume of.

caustic sodasolution (38' Be); :The solution is then filtered oil from the iron residue and introduced into an excess oi cold "dilute hydrochloric acid. The bis- (3-amino-benzene-sultonyl) benzidine-m.m'-disulionic acid oi the formula: sod! Y form of its calcium salt separates in a granular is precipitated. It ll isolated in the ma 'ner by'illtering of! and-dried. In this form it is a white powder soluble in hot water with a mineral acid reaction to Congo paper. It ki'orins a yellowish colored tetrazo compound when tetrazotiited-.,diilicultly=-soluble in cold water.

' A quantity of this compound corresponding one gram molecule isdissolved by theaddition of 100 parts by weight of chalk in about 7 times the quantity of hot water. Into the well stirred solution are introduced 400 parts by weightoi' chalk and at a temperature of 85-90 C. 638 parts by weight of 1.2-dichlorobenzene-4-suliochloride (130% 01' the theoretical amount) The reaction begins ai'ter a short time and the condensation "product separates first in an oily and finally in a stable form. The temperature is kept for some time at 90-95 C. and then the mixture is boiled iorhalf an hour; After cooling the solution is removed from tlie stable precipitate which is treated with dilute'hydrochloricacid at a temperature of 60-70 C. The acid solution containing calcium chloride is filtered 01! and the realdue is dissolved in ten times the quantity 0! hot water with the addition of sodium carbonate. The calcium carbonate which precipitates is illtered oil and the solution thus obtained is acidifled with dilute acetic acid. After cooling the "solution the bis-(l.Z-dichlorobenzeneA-suli'ttnyl- '3"-aminobenzene -1- sulionyl) benzidine-disule, ionic acid separates in the form 0! its sodiumsalt oi the formula: I

"SOsNI OtNa in a Wu and then in a granular tormandmay be'isolatedby filtering oil. The dried product is a white powder easily soluble'in warm water-and being precipitated by "common salt or acids.

when this substance imadded to a dyeing-bath in which-halt wool or half silk is intended to be dyed-with a substantive dyestufl, it reserves the wool or the silk to a high degree from becoming,

dyed- A I The lfl-dichlorobenzene-i sulfochloride used in the receding-Examples 4 and 5 for the prepara' on of the; condensation products containing systems '01 T6 nuclei can also be replaced by othersubstituted or unsubstituted arylsulfo (naphthalene 1 --su1ionyl- 3' aminobenzene-l sul1onyl)-benzidine-m.m-disuli'onic 'acid of the formula:

and the'sodiurn salt oi thebiS-(naphthalene-Z- sulionyl.-3'- aminobenzene -1'- sultonyl) -be'nzi-v dine-m.m'-disultonic acid of the formula:

S OsNli are "also valuable reserving agents for wool or silk against substantive dyestuffs. These compounds may be prepared by combining bis-(3- aminobenz'ene- 1 -sulfonyl) -benzidine-m.m' -disultonic acid with naphthalene-l-suliochloride or replaced by carbonimido groups.

to the probable formula:

naphthalene-Z-sulfochloride, respectively.

Furthermore, the, sulifonlmido groups can be Such compounds are, for instance, the bis-(benzoyl-3'- aminobenzene -1'- sulfonyl)benzidine-mm-d.isultonic acid which corresponds in the form of its sodium salt to the following probable formula: 1

S OsNB NH om; I 7 NH .oo $0 orv the bis-(1.2-dichlorobenzene-4-sulfonyl 3'- aminobenzoyl)-benzidine-m.m'-disulfonic acid which corresponds in the form of its sodium salt SOsNa Both these compounds may be produced-by combining two molecules of benzoylchloride with one molecule of bis-(3-aminobenzene-l-sulfonyl)- -benzidine-m.m'-disultonic acid respectively by combining two molecules oi'lQ-dichIcro-benzenei-sultochloride with onemolecule oi bis- (Ii-aminochlorides. For instance, the sodium salt 0! bisbenzoyl)-benzidine-m;m'-disul1onicacid.; These products .are likewise valuable reserving "agents for wool or silk against substantive dyestufls.

Iaa'mple 6.'1he quantity corresponding to one gram molecule ol bis-(3-amin9benzene-1-suli'onyll-benzidine-mm' dis'ultonic acid in the form of its sodium salt is dissolved in about 10 NILSO:

timesthe quantity of hot water with the addition of 100 parts by weight of chalk. Into the well stirred solution are introduced 400 partsby weight of chalk and at Bil-85 0-. 554 parts by weight of meta-nitrobenzene suliochloride (125% of the theoretical amount)-. It is heated at 90 C.

for some time and boiled for half an hour. After cooling the solution is filtered of! from the resi-' due and the latter is treated withdilute hydrochlorlc acid at 60-70 Q. The acid solution containing calcium chloride is removed and the brown colored residue'is dissolved 1520 times the quantity 01' hot water. Into this solution heated to 90 C. are introduced 200 parts by volume of hydrochloric acid and 1000 parts by weight Cl of iron powder, and the reduction mixture is kept boiling for 2 to 3 hours. The reduction solution is then rendered strongly alkaline with 600 parts by volume of caustic soda lye (38 Be.) and the 'solution is filtered oil from the iron residue. Alter cooling the bis-(3-ami nobenzene 1-sultonyl-3'- After sodium carbonate;

aminobensine-l' smiooyl) '-bcnsidine msa' 1. sulionic acid of the formula:

separates from the solution on acidying it with crude hydrochloric acid. This compound "is a white powder soluble in hot water: the tetrazotized compound is yellowish colored and diiilcultiv solu-. bleincold water.

l The quantity corresponding to one gram molecule of bis-(fl-aniinobenzene-l-sulionyl-3'- aminobenzene-P-sulicnyl) -benzidine mm di-L- suli'onic acid is then dissolved in about 15 times the quantity oi hot water with the addition of 220 parts by weight of chalk. Into the well stirred J solution are introduced 400 parts by weight of chalk. and afterwards at 85-95 0. cas parts in weight o1 1.2-dichlorobenzene-4-suli'ochloride.

e reaction is completed the mint is boiled for about half an hour. After cooling the solution is filtered on! from the residue representing a compact mass and the latter is treated with an excess of dilute hydrochloric acid at C. The acid solution containing calcium chloride is removedand the condensation product is dissolved while heating in an aqueous solution. of v The solution removed by filtration from theprecipitated calcium carbonate is then rendered strong acid by the addition of dilute acetic acid. The sodium salt 01 bis-l-z-dichlorobenzene-4-sulfonyi- 3'- aminobenzene i'- suli'onyl -3"-aminobenzene l"- sulionyl) beanidine-mm'-disulionic acid corresponding to the formula:

- QOiNa is almost quantitatively precipitated from the 'solution and-can be isolated by illtering gfl' from the cooled aqueous solutionfiTheiew product easily soluble in warm water-is able in a high degree to reserve wool or silk in" mixed textilefabrics from becoming dyed by substantive dyestuffs. In the Examples 2-6 the starting materiaL- the behzidine-m.m'-disulionic acid, can be replaced for 'example by 'tolidlne-m.m'-disulionic acid or diaminostilbene'-m.m'-disulionic acid or by diaminodiarylderivatives having other bridge-bonds between the two aryl nuclei. In an analogous acvdaov I manner diaminobenaene derivatives such as Bidtoluylcn'ediaznine-t-sul ionieacid or 2.4-toluylenev diamine-d-suifonic add so on may be used 15 as starting materials instead of the above mentioned diaminodiphenyl derivatives. The condensation products thus obtained likewise possess the properties of reserving 'wool or silk Irom'be- V coming dyed by substantive dyestufls.

Example 7.--a1a parts fby weight of 1.5-naphthylenediamine-SJl-disulfonic acid are dissolved in about 15 times the quantity of water with the addition 91,180 parts'by. weight 01 sodium carbonate. -While heating after theaddition of about 250 parts by weight oi chalk 886 parts by weight of 3-nitrobenzene-sultochloride (200% of the the oretical amount) are introduced at 0. into the solution. While well stirring this solution is kept I for some time at 85-95 C., and then it is further boiled for abouthali' an hour. When coolingthe solution is rendered Congo acid by the addition 01' hydrochloric acid and the condensation product thus obtained is further precipitated by an addition of common salt. It is filtered off, washed with dilute. hydrochloric acid and reduced at boiling temperature with a' calculated quantity of a concentrated solutionoi' stannous'chloride in hydrochloric acid. The bis-(3-aminobenzene-lsulfonyl(-1'.5'-naphthylene-3'.'l'-disulionic acid is separated after cooling. This compound is redissolved in a sodium carbonate solution and precipitated from the filtered solution by the addition 7 oil acetic acid; The quantity corresponding to one gram molecule of this compound is dissolved in aboutlii times thequantity at hot water with the addition of parts by weight oi chalk. Into the well stirred solution are introduced at 85-95? 0.459 parts by weight of benzene suli'ochloride oi the theoretical amount). when the reaction is finished, it is boiled for about half an hour, while well stirrfng,.then it is cooled and the solution is filtered of! from the reaction product remaining in form of a compact mass. To this mass a hot solution of sodium carbonate is added, the resulta ing lye is filtered to remove the calcium carbonate, and the condensation productis precipitatedby the addition 01 acetic acid. Thus the sodium salt of the bis-(benzenesulionyl-3'-aminobenzene 1'- sulionyl) -1".5"-naphthylenediamine-3".7" disulionic acid of the formula:

S'OsNl can oi' ths group consisting oi 0,-1. and 2, said oompounds being colorless or nearly colorless powders, soluble in water, and being valuable reserving agents i'or wool or silk dyestufls.

d I '0: Qsoom m! some i 7 mom-O is obtained flrstly in a' viscous andthen alter cooling in a crystalline form. when dried it' represents a white powder. easily soluble in hot water, which partly precipitates, when the solution is cooled. I

It is capable to a high degree of reserving woo or silk against substantive dyestufls. We claim:

1. Substituted arylaoidylamino compounds selected irom the class consisting of y mz-(sol-m-nmn-solm I v j snqsm-ar-Nmn-som NHL-(C 0-Br-NHTIl -C 0 It:

wherein Y stands for an aromatic radical oi the group consisting of phenylene, naphthylene, di- -phenylene and compounds in which two benzene nuclei are'linked together by means of a bridge,

each benzene nucleus being substituted by a sulionic acid group. R1 and R2 stand for a benzene nucleus having the acyia'mino groups in metaposition to each other and R: and R4 stand for nuclei of thegroup consisting. of benzene and naphthalene nuclei n being a number of the group consistingof 0, 1, and 2,'said compounds being colorless or nearly colorlesspowders, soluble in water, and being valuable reserving agents 10: wool or silk against substantive dyestuiis.

2. Substituted arylacidylamino compounds selected from the class consisting oi in which Y denotes an aromatic radical in which two benzene nuclei are linked together by means 0! a bridge, each nucleus being substituted by a sulionic acid group, R1 and R: denote a benzene nucleus having the acylamino groups attached to it in meta-position to each other and R: and R4 denote nuclei of the group consisting of benzene and naphthalene nuclei n bei g imlmber 3. Substituted arylacidylamino compounds selooted from the class consisting of in which Y denotes a diphe'nylene nucleus each benzene nucleus thereof :beingsubstitnted by a sulionic acid group. R1 and R: denote a benzene nucleus having the acylamino BI'O D attached to it in meta-position to each other and R: and R4 denote nuclei of the group consisting oi! benzene and naphthalene nuclei. 1: being a number of the-group consisting of 0, '1, and'2, said compounds being colorless or nearly colorless powders, soluble in water, and being valuable reserving agents for wool or silk against substantive dyestuffs.

4..A condensation product having the forthat producfbeing a colorless powderl easily soluble in water and being a valuable reserving agent for wool or silk against substantive dyestufls.

a ainst substantive 5Q Condensation products of the general tormula: V

NH-(B -Ri'-NmIB0r R$ 6. The products defined in claim wherein a chlorine atom is in meta-position to the sultonic amide group.

7. Condensation products of the general formula:

- NH-(S Og-E-fliHMl-SOg-Bn Nn(so|n,-NH n-s0.m v NH (S0r--R:-NK)n--B0rR4 in which Y- denotes an aromatic radical of the in which Y denotes an aromatic radical of the group consisting of di-phenylene and compounds group consisting of di-phenylene and compounds in which two benzene nuclei are linked together in which two benzene nuclei are linked together 0 by means of a bridge, each nucleus being subby means of a bridge, each nucleus being sub- 10 stituted by a sulionic acid group, R1 and B: destituted by a sulfonic acid group, R1 and R: are

note a benzene nucleus having the S0: and NH benzene nuclei having the SO: and NIH-groups atgroups attached to it in metaposition to each tached to them in meta position to each other, other and R; and R4 denote nuclei of the group and R: and R4 are benzene nuclei substituted at consisting of benzene and naphthalene 7 nuclei. least in meta position to the amide group by chlo- 1.,

, said nuclei R: and R4 being substituted by chlorine, n being a number of the group consisting of rine, n being 0, 1 or 2; said condensation prod- 0, 1 and 2, said condensation products being ucts being colorless'or nearly colorless powders, colorless or nearly colorless powders soluble in soluble in water, and being valuable reserving water. and being valuable reserving agents for '20 agents for wool'or silk against substantive dvewool or silk against substantive dyestufls.

JOHANN msmmz. mrqo scrrwnrrznn.

csarrnci'rs lorconsor ium,

ru No. 2,070,207. I l-"e bruari 9 1937'. 1'

Jus ina Heisman, "in in;

.I'tiahereby certified that the above nugbe'red patent was erroneously issued to 'i. G. Farbe'nindustrie Aktiengeeeiiachait" whereas eaidpatent should have been issued to General Aniline Works Inc. 0t Rel-York; I I

N. Y. as aseignee by me sne assignments, as shown by the records 6: assignments in this office; and that the eiiid Letters Patent should be I read with thiacorrection therein that the cane may conform to the record (Seal) I or the ease in the PatentOffice.

Signed e sealed this t day at Ma A; b. 1937.

5Q Condensation products of the general tormula: V

NH-(B -Ri'-NmIB0r R$ 6. The products defined in claim wherein a chlorine atom is in meta-position to the sultonic amide group.

7. Condensation products of the general formula:

- NH-(S Og-E-fliHMl-SOg-Bn Nn(so|n,-NH n-s0.m v NH (S0r--R:-NK)n--B0rR4 in which Y- denotes an aromatic radical of the in which Y denotes an aromatic radical of the group consisting of di-phenylene and compounds group consisting of di-phenylene and compounds in which two benzene nuclei are linked together in which two benzene nuclei are linked together 0 by means of a bridge, each nucleus being subby means of a bridge, each nucleus being sub- 10 stituted by a sulionic acid group, R1 and B: destituted by a sulfonic acid group, R1 and R: are

note a benzene nucleus having the S0: and NH benzene nuclei having the SO: and NIH-groups atgroups attached to it in metaposition to each tached to them in meta position to each other, other and R; and R4 denote nuclei of the group and R: and R4 are benzene nuclei substituted at consisting of benzene and naphthalene 7 nuclei. least in meta position to the amide group by chlo- 1.,

, said nuclei R: and R4 being substituted by chlorine, n being a number of the group consisting of rine, n being 0, 1 or 2; said condensation prod- 0, 1 and 2, said condensation products being ucts being colorless'or nearly colorless powders, colorless or nearly colorless powders soluble in soluble in water, and being valuable reserving water. and being valuable reserving agents for '20 agents for wool'or silk against substantive dvewool or silk against substantive dyestufls.

JOHANN msmmz. mrqo scrrwnrrznn.

csarrnci'rs lorconsor ium,

ru No. 2,070,207. I l-"e bruari 9 1937'. 1'

Jus ina Heisman, "in in;

.I'tiahereby certified that the above nugbe'red patent was erroneously issued to 'i. G. Farbe'nindustrie Aktiengeeeiiachait" whereas eaidpatent should have been issued to General Aniline Works Inc. 0t Rel-York; I I

N. Y. as aseignee by me sne assignments, as shown by the records 6: assignments in this office; and that the eiiid Letters Patent should be I read with thiacorrection therein that the cane may conform to the record (Seal) I or the ease in the PatentOffice.

Signed e sealed this t day at Ma A; b. 1937. 

